Padding dried reactive dye impregnated cellulose textiles with sodium silicate, 48-52deg baume, for low temperature batch fixation



United States Patent 3 416 876 PADDING DRIED REXCTI VE DYE IMPREGNATED CELLULOSE TEXTILES WITH SODIUM SILI- CATE, 48-52" BAUME, FOR LOW TEMPERA- TURE BATCH FIXATION Hans Ohmer, Neu-lsenburg, Germany, assignor to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed Jan. 3, 1968, Ser. No. 695,337 Claims priority, application Germany, Jan. 10, 1967, F 51,213 7 Claims. (Cl. 854.2)

ABSTRACT OF THE DISCLOSURE The invention includes the step of printing a sulfone ethyl sulfate ester of an azo dye on a cellulose fabric,

drying the fabric, then padding the fabric with 4852 Baum liquid sodium silicate and then batching the fabric for a cold dwell development of hours at room temperature. The fabric is washed with sodium metaphosphate solution and then soaped with a synthetic detergent. The batched fabric can be heated to 40-50 C. to facilitate dye fixation.

Other reactive types of dyes such as vinyl sulfone, chlorotriazine, dichloroquinoxaline, 2,2,3,3 tetrafluorocyclobutane 1 acryloylamine and phenylsulfene propionylamine type dyes can be used in this process. Also nonreactive dyes with reactive hydrogens can be printed with reactive compounds such as 1,3,5-tri(acryloyl)hexahydros triazine, methylene-bisacrylamide and 2,4,6-triethylimino-s-triazine in this process.

It is known that reactive dyestulfs can be fixed fast on textile materials of native or regenerated cellulose with the aid of alkalis or alkali-forming compounds. The choice of the alkaline substances or the alkali-forming compounds depends on the nature of the reactive groups contained in the dyestuffs used and further on the nature of the fibres to be dyed as well as on the application process intended.

According to the known two-phase printing processes fast fixation of the reactive dyestufif on textile material of native or regenerated cellulose is carried out in that the dyestuff is applied to the fabric in the first step by means of a printing" paste which contains water and a thickening agent which is incapable of reacting, and then, in the second step, the thus obtained print, after drying, is impregnated with an aqueous, more or less strong alkaline, salt-containing bath and subsequently fixed by the action of heat (two-phase steaming process), or is fixed by dipping it into the alkaline bath at boiling temperature (wet fixation process), or is padded with the alkaline bath and fixed according to the cold dwell method.

When using alkaline, salt-containing aqueous baths as fixing agents, unimportant variations of the concentrations of the bath, of the fixation period and of the temperature may have negative eifects on the yield of the dyestutf and on the appearance of the prints. When using alkali in the form of 100 ml. of sodium hydroxide solution of 28 B. per litre of salt-containing padding liquor as is the case in the pad-air-passage process and in the cold dwell process some dyestuffs partially hydrolyze during the necessary fixation period which becomes evident in changes of the shade as for example with the copper complex compounds of the dyestulf of the formula Now it has been found that reactive dyestufis can be fixed fast on textile materials of native or regenerated cellulose by printing on the textile material either an organic dyestufi which contains at least one fi-hydroxyethylsulfone sulfuric acid ester group, vinylsulfone group, monochlorotriazine group, dichlorotriazine group, 2,2,3,3- tetrafluorocyclobutane l-acryloylamino group, vinylsulfonylamino group, pi-hydroxyethylsulfonylamino sulfuric acid ester group, 13-phenylsulfonylproprionylamino group or dichloroquinoxaline radical, or an organic dyestutf containing at least one nucleophilic group and a colorless organic compound containing at least two reactive groups, which groups are capable of reacting With the fiber as well as with the nucleophilic groups of said dyestuffs, by means of a printing paste which further contains water and a thickening agent, then impregnating the print so obtained, after drying, with a liquid alkali metal silicate of the concentration of about 48 to about52 B. at a pH-value of about 11 to 12, and subsequently dwelling it at temperatures between 10 and 30 C., preferably at room temperature. Preferably a liquid sodium silicate is used for the impregnation of the print.

As reactive dyestuffs there can be used according to the process of the present invention dyestuffs from different organic dyestuff classes, for example, azo dyestuffs and anthraquinone dyestuffs, which contain at least one of the above-mentioned reactive groups, or dyestuffs of such kind which-owing to the presence of nucleophilic groupsare capable of reacting with a colorless compound containing at least two reactive groups, said groups being capable of reacting with the fiber as well as with nucleophilic groups in said dyestuffs.

As compounds containing at least two reactive groups which are capable of reacting with the fiber as well as with the dyestuffs containing nucleophilic groups there can be mentioned for example:

(a) 1,3,5 tri r (acryloyl)-hexahydro-s-triazine of the formula (b) Methylene-bisacrylic acid amide of the formula NHC OCH=CH2 NH-C 0oI-I=oH2 (c) 2,4,6-triethyleneirnino-s-triazine of the formula As dyestuffs capable of reacting with the colorless compounds containing at least two reactive groups preferably dyestuffs of the azoand anthraquinone-series are ap propriate which contain as nucleophilic groups, for example, sulfonic acid amide groups, N-mono-substituted sulfonic acid amide groups, hydroxy groups, mercapto groups and/or acetoacetyl groups and/or heterocyclic ring systems containing imino groups.

The optimum concentration of liquid alkali metal silicate and the dwelling period which has to be applied within the scope mentioned in the individual cases must be adapted to the respective reactive dyestutf used and to the amount of this dyestuff which is to be fixed.

Of the liquid alkali metal silicates (water-glasses) which are used according to the process of the present invention preferably liquid sodium silicate (soda waterglass) of the above-mentioned concentration and pH-- range and of a density of about 1.48 to about 1.55 as well as of a proportion by weight of Na O:SiO of 1:2.1 to 1:3 is applied.

When impregnating according to the process of the present invention the temperature of the alkali metal silicates used may be, for example, room temperature. Depending on the mode of the impregnation applied, it may be of advantage to use alkali metal silicate having a slightly elevated temperature, for example about 4050 0, because at increased temperatures the viscosity of the alkali metal silicate is correspondingly reduced and it can thus be handled more easily.

Suitable thickening agents are neutral, weakly alkaline or weakly acid reacting thickening agents such, for example, as alginates, various types of gum, alkyl celluloses or hydroxyethyl celluloses, as well as mixtures thereof and even emulsions or semiemulsions prepared from the thickeners with the aid of appropriate emulsifiers.

The technical advantage achieved with the application of the liquid alkali metal silicate as fixing agent lies in the fact that sources of errors which are possible when preparing the commonly known aqueous fixing baths do not occur, that an excellent reproducibility of the tints is guaranteed, that the yield of dyestuff being fixed is throughout superior to the known similar processes, and that the prints do not suffer a change in the tint and do not flow during the dwelling period. Furthermore, it is advantageous, that the impregnation of the primary prints with the alkali metal silicates is not limited to the paddyeing but can also be carried out by slop-padding, nippadding, over-printing by means of hatching rolls or screen printing machines, dipping or manual application. Besides, a considerably greater number of dyestuffs can be applied for the present process as is the case in connection with the known padand air-passage process and the cold dwell process, which methods work with an aqueous saltand alkali-containing bath.

The liquid alkali metal silicates used according to the process of the present invention are not dyed when impregnating the primary prints, whatever form of impregnation is applied, since the dyestuffs used are not soluble into the alkali metal silicate.

The following examples serve to illustrate the invention but they are not intended to limit it thereto; the parts being by weight unless otherwise stated.

EXAMPLE 1 40 parts of the dyestutf of the formula are dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% strength which contains 5 parts of a complex forming agent on the basis of polymeric sodium metaphosphate per 1000 parts of thickener.

After addition of parts of the sodium salt of metanitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of 245 parts of water or 245 parts of an aqueous alginate, thickener of 4% strength, depending on the viscosity required,

The thus prepared printing paste is printed on a fabric consisting of cotton, staple fiber or rayon by means of a cylinder printing machine. After drying, the printed fabric is padded with liquid sodium silicate of 48-52 Baum and it is batched or cuttled up, allowed to dwell for about 5 hours at room temperature, without interposition of an air passage or intermediate drying.

The thus obtained print is then rinsed in warm water baths at a temperature of 40 C. until the baths show a neutral reaction. Thereupon, the print is treated for some minutes with water of about 60 C., the water containing 3 parts of a complex forming agent on the basis of a polymeric sodium metaphosphate per 1000 parts by volume, subsequently it is soaped for about 10 minutes with a 1% aqueous solution of a synthetic detergent (sodium salt of the condensation product of oleic acid and N-methyl taurine) and finally rinsed and dried.

There is obtained a yellow print having good fastness to light and to wet processing.

Silicates dried-in on the fabric may easily be dissolved and washed out again by means of warm water, if they are decomposed by the carbon dioxide of the air or by means of a sodium hydroxide solution or hot soda solution.

EXAMPLE 2 parts of the dyestutf of the formula S|O Na are dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% strength which contains 5 parts of a complex forming agent on the basis of polymeric sodium metaphosphate per 1000 parts of thickener.

After addition of 15 parts of the sodium salt of metanitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of 245 parts of water or 245 parts of l SOaNtL EXAMPLE 3 40 parts of the dyestufi? of the formula 6 EXAMPLE 5 40 parts of the cobalt complex compound of the dyestuff of the formula NaOiS HO are dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% strength which contains 5 parts of a complex forming are dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% strength which contains 5 parts of a complex forming agent on the basis of polymeric sodium metaphosphate per 1000 parts of thickener.

After addition of 15 parts of the sodium salt of metanitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of 245 parts of water or 245 parts of an aqueous alginate thickener of 4% strength, depending on the viscosity required.

The thus prepared printing paste is printed on a fabric consisting of cotton by means of a cylinder printing machine. After drying, the printed fabric is padded with liquid sodium silicate of 4852 Baum and of a temperature of 45 C. and it is batched or cuttled up, allowed to dwell for about 5 hours at room temperature, without interposition of an air passage or intermediate drying.

After an after-treatment of the fabric as described in Example 1 there is obtained an orange print having good fastness to light and to wet processing.

EXAMPLE 4 40 parts of the dyestufi of the formula are dissolved in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% strength which contains parts of a complex forming agent on the basis of polymeric sodium metaphosphate per 1000 parts of thickener.

After addition of parts of the sodium salt of metanitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of 245 parts of water or 245 parts of an aqueous alginate thickener of 4% strength, depending on the viscosity required.

The thus prepared printing paste is printed on a fabric consisting of staple fiber by means of a cylinder printing machine. After drying, the printed fabric is padded with liquid sodium silicate of 4852 Baum and it is batched, or cuttled up, allowed to dwell for about 5 hours at room temperature, without interposition of an air pass-age or intermediate drying.

After an after-treatment of the fabric as described in Example 1 there is obtained a blue print having good fastness to light and wet processing.

agent on the basis of polymeric sodium metaphosphate per 1000 parts of thickener.

After addition of 15 parts of the sodium salt of metanitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of 245 parts of water or 245 parts of an aqueous alginate thickener of 4% strength, depending on the viscosity required.

The thus prepared printing paste is printed on a fabric consisting of cotton by means of a cylinder printing machine. After drying, the printed fabric is padded with liquid sodium silicate of 4852 Baum and it is batched or cuttled up, allowed to dwell for about 10 hours at room temperature.

After an after-treatment of the fabric as described in Example 1 there is obtained a black print having good fastness to light and to wet processing.

EXAMPLE 6 40 parts of a mixture of the dyestuffs of the formulae N...('J\1...N/

| N I l N N 305MB.

and

NaOS N N l N...Cu...N I N N 1 1 S0 Na 3 hao s (R represents herein the grouping are dissolved, after mixing with parts of urea, in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% strength which contains 5 parts of a complex forming agent on the basis of polymeric sodium metaphosphate per 1000 parts of thickener.

After addition of 15 parts of the sodium salt of meta- 7 nitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of 145 parts of water.

The thus prepared printing paste is printed on a fabric consisting of cotton or staple fiber by means of a cylinder printing machine. After drying, the printed fabric is nippadded with liquid sodium silicate of 4852 Baum and it is immediately allowed to dwell for about 10 hours at room temperature. 1

After an after-treatment of the fabric as described in Example 1 there is obtained a turquoise print having good fastness to light and to wet processing.

EXAMPLE 7 40 parts of a mixture of the dyestuffs of the formulae NaO S N in... l

(R represents herein the grouping are dissolved, after mixing with 100' parts of urea, in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% strength which contains 5 parts of a complex forming agent on the basis of polymeric sodium metaphosphate per 1000 parts of thickener.

After addition of 15 parts of the sodium salt of metanitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of 145 parts of water.

The thus prepared printing paste is printed on a fabric consisting of cotton by means of a cylinder printing machine. After drying, the printed fabric is padded with liquid sodium silicate of 4852 Baum and it is rolled up immediately and allowed to dwell for about hours at room temperature.

After an after-treatment of the fabric as described in Example 1, there is obtained a turquoise print having good fastness to light and to wet processing.

EXAMPLE 8 40 parts of the dyestutf of the formula SOaNa OH HCOCH=CHCHCH2 I I I no or: o1 N=N fi 0113 NaOsS SOgNa After addition of 15 parts of the sodium salt of metanitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of 245 parts of water or 245 parts of an aqueous alginate thickener of 4% strength, depending on the viscosity required.

The thus prepared printing paste is printed on a fabric consisting of cotton by means of a screen printing ma chine. After drying, the printed fabric is padded with liquid sodium silicate of 52 Baum and it is allowed to dwell for about 5 hours at room temperature without interposition of an air passage or intermediate drying.

After an after-treatment of the fabric as described in Example 1 there is obtained a red print having good fastness to light and to wet processing.

EXAMPLE 9 40 parts of the dyestuff of the formula l SOgNZt are dissolved, after mixing with parts of urea, in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% strength which contains 5 parts of a complex forming agent on the basis of polymeric sodium metaphosphate per 1000 parts of thickener.

After addition of 15 parts of the sodium salt of metanitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of parts of water.

The thus prepared printing paste is printed on a fabric consisting of cotton by means of a cylinder printing machine. After drying, the printed fabric is padded with liquid sodium silicate of 48--52 Baum and it is batched or cuttled up, allowed to dwell for about 5 hours at room temperature, without interposition of an air passage or intermediate drying.

After an after-treatment of the fabric as described in Example 1 there is obtained a scarlet red print having good fastness to light and to wet processing.

EXAMPLE 10 40 parts of the dyestuff of the formula NaOaS SOaNa are dissolved, after mixing with 100 parts of urea, in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% strength which contains 5 parts of a complex forming agent on the basis of polymeric sodium metaphosphate per 1000 parts of thickener.

After addition of 15 parts of the sodium salt of metanitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of 145 parts of water.

The thus prepared printing paste is printed on a fabric consisting of cotton or staple fiber by means of a cylinder printing machine. After drying the printed fabric is padded with liquid sodium silicate of 48-52 Baum and it is batched or cuttled up, immediately allowed to dwell for about 5 hours at room temperature.

After an after-treatment of the fabric described in Example 1 there is obtained a red print having good fastness to light and to wet processing.

9 EXAMPLE 11 40 parts of the dyestufi of the formula SOsNa are dissolved, after mixing with 100 parts of urea, in 300 parts of hot water and introduced into 400 parts of an aqueous alginate thickener of 4% strength which contains 5 parts of a complex forming agent on the basis of polymeric sodium metaphosphate per 1000 parts of thickener.

After addition of 15 parts of the sodium salt of metanitrobenzene sulfonic acid the whole is made up to 1000 parts by addition of 145 parts of water.

The thus prepared printing paste is printed on a fabric consisting of cotton or staple fiber by means of a cylinder printing machine. After drying, the printed fabric is nippadded with liquid sodium silicate of 4852 Baurn and it is immediately allowed to dwell for about hours at room temperature.

After an after-treatment of the fabric as described in Example 1 there is obtained an orange print having good fastness to light and to wet processing.

I claim:

1. A process for fast fixing reactive dyestuffs on textile materials made of native or regenerated cellulose fibers, which comprises printing on said textile materials a printing paste containing a neutral to weakly alkaline thickening agent, water and either an organic dyestuff containing at least one B-hydroxyethylsulfone sulfuric acid ester group, vinylsulfone group, monochlorotriazine group, dichlorotriazine group, 2,2,3,3-tetrafluorocyclobutane-1-acryloylamino group, vinylsulfonylamino group, ,B-hydroxyethylsulfonylaminosulfuric acid ester group, fi-phenylsulfonylpropionylamino group or dichloroquinoxaline radical, or an organic dyestuif containing at least one nucleophilic group and a colourless organic compound containing at least two reactive groups, which groups being capable of reacting with the fiber and with the nucleophilic groups of said dyestuff, then impregnating the print so obtained, after drying, with a liquid alkali metal silicate having a concentration in the range of from 48 to 52 B. at a pH-value ranging from 11 to 12, and subsequently dwelling the fabric batched or cuttled up at temperatures ranging from 10 to 30 C.

2. A process as claimed in claim 1, wherein as alkali metal silicate a liquid sodium silicate of a density in the range of from 1.48 to 1.55 and of a proportion by weight of Na O:SiO of 122.1 to 1:3 is used.

3. A process as claimed in claim 1, wherein an alkali metal silicate of room temperature is used.

4. A process as claimed in claim 1, wherein an alkali metal silicate of a temperature ranging from 40 to C. is used.

5. A process as claimed in claim 1, wherein dwelling of the print is effected at room temperature.

6. A process as claimed in claim 1, wherein dwelling of the print is effected for a period of time in the range of from 3 to 48 hours.

7. A process as claimed in claim 6, wherein dwelling of the print is effected for a period of time in the range of from 5 to 24 hours.

References Cited UNITED STATES PATENTS 2,892,670 6/1959 Alsberg 8-39 3,183,224 5/1965 Benz et a1 260-146 3,232,926 2/1966 Randall 260-154 FOREIGN PATENTS 934,391 8/1963 Great Britain. 875,862 8/1961 Great Britain.

OTHER REFERENCES Rose: The Condensed Chemical Dictionary, page 1053, 6th edition, published 1961 by Reinhold Publ. Corp., New York.

NORMAN G. TORCHIN, Primary Examiner.

DONALD LEVY, Assistant Examiner.

US. 01. X.R.

s-s 2, s5

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,416 ,876 December 17 1968 Hans Ohmer It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 7, lines 28 to 39, the portion of the formula reading .Cu. should read .(llu. /N\ same column 7 lines 65 to 70 the portion of the formula reading -CH CH-"-CH l should read I I Column 8, lines 18 to 28, the formula should appear as shown below SO Na H co- N=N SO Na Attesting Officer Column 9, lines 3 to 8, the right-hand portion of the formula should appear as shown below:

A N N L A- c1 Signed and sealed this 24th day of March 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR.

Commissioner of Patents 

